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In 1971 he graduated from the Kiev Technological Institute of Light Industry with the specialty of chemical engineer. He served in the KGB of the Soviet Union since that year. In 1972, Radchenko finished the higher courses of the KGB of the USSR in Minsk. Since September of that year, he worked in the KGB directorate for Kiev and the Kiev Oblast. He held supervisory positions and eventually became the chief of a department. From March 1982 until October 1990 — he served in the KGB directorate in the Rivne Oblast in the same positions. In 1986 he graduated from the Higher Red Banner School of the KGB. In 1990, as a supporter of the idea of an independent Ukraine, Radchenko was removed from active service and placed in the reserves.

In the summer of 1991, Colonel V. Radchenko was returned to active service and in July of the year became the deputy head of the KGB directorate in the Rivne Oblast, promoted to major general. From January 1992 he was the chief of the Security Service of Ukraine (SBU) regional directorate in the Ternopol Oblast. From August 1993, Radchenko was the chief of the SBU Directorate for Combating Corruption and Organized Crime. Since March 1994 he was the deputy head of the SBU and chief of Directorate for Combating Corruption and Organized Crime, promoted to lieutenant general. He was considered to be a protege of Yevhen Marchuk.

In early July 1994 Radchenko was selected by the President of Ukraine, Leonid Kuchma, as interim Minister of Internal Affairs, and at the end of the month had "interim" removed from his title. From July 1995 until April 1998 he headed the SBU. In his final year in that position, Radchenko was promoted to General of Army of Ukraine. Since 1996, he had been a member of the National Security and Defense Council of Ukraine, a member of the Coordinated Committee for Combating Corruption and Organized Crime (since 1994), member of the Council for Protecting the National Cultural Heritage (since 1997), member of the Coordinated Council for Judicial Reforms under the President of Ukraine (since 1997).

In April 1998, Volodymyr Radchenko wrote a letter of resignation due to personal reasons and became the first deputy of the Secretary of the National Security and Defense Council, Volodymyr Horbulin. After the Cassette Scandal, President Kuchma again selected Radchenko to be the Head of the Security Service of Ukraine, for the second time. He replaced Leonid Derkach. From February 2001 until September 2003, he held that position. Radchenko was considered to be a professional, not involved with any criminal-finance groups.

From September 2003, he had been the Secretary of the National Security and Defense Council (the position was vacant since the end of June of that year since the appointment of Yevhen Marchuk as the Minister of Defense). In May 2004, V. Radchenko was in the center of attention due to the "cassette scandal:" a Ukrainian businessman accused him and several others in knowing that the cabinet of the President was being recorded. His resignation from Secretary of the Council was accepted in January 2005 by President Kuchma.

From August 2006, he was an adviser of the SBU head, and in November of that year Prime Minister of UkraineViktor Yanukovych named him his adviser. Since 12 January to 25 May 2007 he was the First Vice Prime Minister of Ukraine. Radchenko was removed by the parliamentary majority on 25 May at the peak of the political crisis, set on by the battle for power between the ruling coalition and the president's parliamentary opposition. The official reason of the resignation became for personal reasons due claimed "health problems."